US4610723A - Process for leaching sulphide concentrates of the tetrahedrite type containing high concentrations of arsenic and antimony - Google Patents
Process for leaching sulphide concentrates of the tetrahedrite type containing high concentrations of arsenic and antimony Download PDFInfo
- Publication number
- US4610723A US4610723A US06/656,740 US65674084A US4610723A US 4610723 A US4610723 A US 4610723A US 65674084 A US65674084 A US 65674084A US 4610723 A US4610723 A US 4610723A
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- US
- United States
- Prior art keywords
- copper
- tetrahedrite
- iron
- solution
- ferrous sulphate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000012141 concentrate Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 14
- 229910052785 arsenic Inorganic materials 0.000 title claims abstract description 13
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 9
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052969 tetrahedrite Inorganic materials 0.000 title claims description 10
- 238000002386 leaching Methods 0.000 title claims 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000010949 copper Substances 0.000 claims abstract description 38
- 229910052742 iron Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 21
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000001301 oxygen Substances 0.000 claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 235000003891 ferrous sulphate Nutrition 0.000 claims abstract description 15
- 239000011790 ferrous sulphate Substances 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001117 sulphuric acid Substances 0.000 claims abstract description 4
- 235000011149 sulphuric acid Nutrition 0.000 claims abstract description 4
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical class [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000002739 metals Chemical class 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims abstract 3
- 230000035484 reaction time Effects 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 2
- 229910052976 metal sulfide Inorganic materials 0.000 claims 2
- 239000011541 reaction mixture Substances 0.000 claims 1
- 238000004064 recycling Methods 0.000 claims 1
- 239000011701 zinc Substances 0.000 abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052725 zinc Inorganic materials 0.000 abstract description 7
- 239000007789 gas Substances 0.000 abstract description 5
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 abstract description 3
- -1 ferrous metals Chemical class 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 abstract description 2
- 239000010941 cobalt Substances 0.000 abstract description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 150000004763 sulfides Chemical class 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 229910052709 silver Inorganic materials 0.000 description 11
- 239000004332 silver Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- 239000012267 brine Substances 0.000 description 9
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 235000020094 liqueur Nutrition 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229960002668 sodium chloride Drugs 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229940000489 arsenate Drugs 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- BMWMWYBEJWFCJI-UHFFFAOYSA-K iron(3+);trioxido(oxo)-$l^{5}-arsane Chemical compound [Fe+3].[O-][As]([O-])([O-])=O BMWMWYBEJWFCJI-UHFFFAOYSA-K 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B17/00—Obtaining cadmium
- C22B17/04—Obtaining cadmium by wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
- C22B19/22—Obtaining zinc otherwise than by distilling with leaching with acids
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Definitions
- invention patent concerns with the hydrometallurgic treatment of concentrates of copper sulphides of the tetrahedral type which contain antimony and arsenic at high concentrations, for the recovery of copper and noble metals.
- the treatment which is here proposed consists in a lixiviation in aqueous medium at a temperature higher than the melting point of sulphur and for low density of pulp, in which a ferrous sulphate solution is used as lixiviating medium, and which purpose is the almost total dissolution of copper from the concentrate and the antimony and arsenic precipitation as iron antimoniates and arsenates, thus producing a rich liquour which contains the copper and sulphuric acid as also the sulphates of the soluble non ferrous metals as zinc, cadmium, cobalt, etc., by which all the metals contained can be recovered after arsenic precipitation and the solution pH settle by conventional methods being the cementation of copper with scrap iron the preferable since it produces the aqueous ferrous solution necessary for the lixiviation; which residue, mainly formed by ferric antimoniate and arsenate, contains the whole silver from the concentrate, which is recovered by lixiviation in sodium chloride solution followed by cementation of the liquid with zinc
- the lixiviation of the concentrate consists in its dispersion into a ferrous sulphate solution for producing a pulp of solid--with fixed and under control density followed by oxidation of that pulp by means of a gas containing oxygen inside a pressured reactor with stirring.
- the ferrous sulphate solution must be to an iron concentration within 1 and 50 g/l, according to the richness of antimony and arsenic existing in the copper concentrate, thus the mass ratio Fe/(As+Sb) is higher than 0.5 and preferably 1.5.
- the pulp density of lixiviation is adjusted depending on the iron concentration in the ferrous sulphate solution, using always quantities higher than 40 Kg of solid by cubic meter of solution but preferably employing 100 Kg/m 3 . This last value improves the energetic balance of the treatment.
- the pulp oxidation temperature must be maintained between 140° and 250° C. and preferably at 220 ⁇ 10° C.
- the working pressure is adjusted considering that is necessary to maintain the partial pressure of oxygen higher than 300 KPAS and preferably 600 ⁇ 100 KPAS.
- the gas preferably employed in the reaction is oxygen, though air and air enriched with oxygen can be also employed.
- the necessary reaction time to complete the oxidizing reaction from sulphides to sulphates, and precipitation of ferric antimoniates, ferric arsenate and ferric oxide are within a minimum of 30 minutes, with a preferably value of 60 minutes. Therefore the stay time in the reactor will be the equivalent to the mentioned reaction time.
- the equipment inside of which the reaction takes place may be a horizontal reactor of compartmented type or a cascade vertical-type, which can be stirred mechanically or by gas, and can be continuous or discontinuous, though the cost of the process probably will be lower with the continuous type.
- copper may be dissolved in aqueous medium with a yield higher than 95%.
- Silver remains in the solid residue together with antimonium, arsenic and iron. That residue is highly crystaline wherefore can be easily decanted and filtered.
- the copious liqueur with a residual sulphuric acidity within 15 and 30 g/l, with less than 0.3 g/l of iron and with 0.5 to 3.0 of arsenic, can be submited to a precipitation treatment of arsenic and later fitting of pH with an alkali.
- the resulting liquid is wholly adequated for recovering the copper either by extraction by solvents or by cementation with scrap iron, though this later technique has the advantage to supply to the solution the necessary iron so that can be recycled to the lixiviation of the concentrate.
- the residue of the lixiviation is treated with a sodium-chloride solution, for giving place to a chloruret complex of silver (AgCl 2 + , AgCl 3 2+ ).
- the solubleness yield in this step is higher than 95%.
- the cementation is initiated using zinc powder as reducing agent.
- the obtained product is a cement with a high silver content.
- the equipment used in the essays are a laboratory reactor of 3.78 l, built in AISI 316L and titanium, with mechanical stirring, electrical sheet heating system, water cooling system through coil, temperature and pressure by automatic control, etc.
- Pulp density 100 Kg/m 3 ; oxygen pressure: 600 KPAS; reaction time: 60 min.; stirring speed: 1300 rpm; iron in liquid: 21.3 g/l; concentrate composition (in percentage): Cu 26.5; Ag 0.27; Sb 13.2; As 6.8; Fe 2.0; Zn 2.9, and S 19.4.
- Pulp density 60 Kg/m 3 ; temperature: 220° C.; reaction time: 60 min.; stirring speed: 1300 rpm; iron in liquid: 25.6 g/l; composition of the concentrate (in percentage): Cu 26.5; Ag 0.27; Sb 13.2; As 6.8; Fe 2.0; Zn 2.9, and S 19.4.
- the values of the established conditions for the essays are the following: Pulp density: 100 Kg/m 3 ; temperature: 220° C.; oxygen pressure: 600 KPAS; reaction time: 60 min.; iron in liquid: 21.3 g/l; composition of the concentrate (in percentage): Cu 26.5; Ag 0.27; Sb 13.2; As 6.8; Fe 2.0; Zn 2.9, and S 19.4.
- Pulp density 60 Kg/m 3 ; temperature 220° C.; oxygen pressure: 600 KPAS; stirring speed: 1300 rpm; iron in liquid: 12.8 g/l; composition of the concentrate (in percentages): Cu 26.5; Ag 0.27; Sb 13.2; As 6.8; Fe 2.0; Zn 2.9, and S 19.4.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Paper (AREA)
Abstract
A process for lixiviation of concentrates of copper sulphides of tetrahedral type containing high concentration of arsenic and antimony to recover copper and noble metals. The concentrates are repulped into an aqueous ferrous sulphate solution with an established and controlled solid-liquid ratio which is thereafter oxidized by an oxygen containing gas in a reactor, thereby oxidizing the sulphides to sulphates, precipitating iron as ferric arsenates and antimoniates and yielding a lixiviation pulp in which the solid phase contains the iron, antimony and arsenic as well as the insoluble sulphates of the non-ferrous metals, such as lead and noble metals, and the liquid phase containing the copper, free sulphuric acid and the soluble sulphates of non-ferrous metals, as well as zinc, cadmium, cobalt, etc. The metals contained therein are recovered, after solid-liquid separation by conventional method. Among them, the copper cementation with scrap iron from the lixiviation liquid is the preferable method, because it yields the necessary aqueous solution of ferrous sulphate for the lixiviation.
Description
The present application of invention patent concerns with the hydrometallurgic treatment of concentrates of copper sulphides of the tetrahedral type which contain antimony and arsenic at high concentrations, for the recovery of copper and noble metals.
This type of copper concentrate, characterized by the high content of arsenic and antimony is heavily punished when it is accepted by the conventional foundries.
On the other side, the principal part of copper in this type of concentrate is present as tetrahedrite, which involves to be very refractory under the conventional hydrometallurgic treatments.
The treatment which is here proposed consists in a lixiviation in aqueous medium at a temperature higher than the melting point of sulphur and for low density of pulp, in which a ferrous sulphate solution is used as lixiviating medium, and which purpose is the almost total dissolution of copper from the concentrate and the antimony and arsenic precipitation as iron antimoniates and arsenates, thus producing a rich liquour which contains the copper and sulphuric acid as also the sulphates of the soluble non ferrous metals as zinc, cadmium, cobalt, etc., by which all the metals contained can be recovered after arsenic precipitation and the solution pH settle by conventional methods being the cementation of copper with scrap iron the preferable since it produces the aqueous ferrous solution necessary for the lixiviation; which residue, mainly formed by ferric antimoniate and arsenate, contains the whole silver from the concentrate, which is recovered by lixiviation in sodium chloride solution followed by cementation of the liquid with zinc powder giving place to silver cement.
The lixiviation of the concentrate consists in its dispersion into a ferrous sulphate solution for producing a pulp of solid--with fixed and under control density followed by oxidation of that pulp by means of a gas containing oxygen inside a pressured reactor with stirring.
The ferrous sulphate solution must be to an iron concentration within 1 and 50 g/l, according to the richness of antimony and arsenic existing in the copper concentrate, thus the mass ratio Fe/(As+Sb) is higher than 0.5 and preferably 1.5.
The pulp density of lixiviation is adjusted depending on the iron concentration in the ferrous sulphate solution, using always quantities higher than 40 Kg of solid by cubic meter of solution but preferably employing 100 Kg/m3. This last value improves the energetic balance of the treatment.
The pulp oxidation temperature must be maintained between 140° and 250° C. and preferably at 220±10° C.
The working pressure is adjusted considering that is necessary to maintain the partial pressure of oxygen higher than 300 KPAS and preferably 600±100 KPAS.
The gas preferably employed in the reaction is oxygen, though air and air enriched with oxygen can be also employed.
During the course of oxidation is necessary to maintain an intense stirring conditions, thus enough dispersion in the oxidizing-gas phase into the liquid phase is achieved, avoiding that the solution of oxygen into the liquid to be the controlling step from the kinetic point of view.
The necessary reaction time to complete the oxidizing reaction from sulphides to sulphates, and precipitation of ferric antimoniates, ferric arsenate and ferric oxide are within a minimum of 30 minutes, with a preferably value of 60 minutes. Therefore the stay time in the reactor will be the equivalent to the mentioned reaction time.
The equipment inside of which the reaction takes place may be a horizontal reactor of compartmented type or a cascade vertical-type, which can be stirred mechanically or by gas, and can be continuous or discontinuous, though the cost of the process probably will be lower with the continuous type.
In these conditions the following main reactions take place:
Cu.sub.8 Sb.sub.2 S.sub.7 +4FeSO.sub.4 +35/2O.sub.2 +3H.sub.2 O→8CuSO.sub.4 +Fe.sub.2 Sb.sub.2 O.sub.7 ↓+Fe.sub.2 O.sub.3 ↓+3H.sub.2 SO.sub.4 ( 1)
Cu.sub.8 As.sub.2 S.sub.7 +4FeSO.sub.4 +180.sub.2 +3H.sub.2 O→8CuSO.sub.4 +2FeAsO.sub.4 ↓+Fe.sub.2 O.sub.3 ↓+3H.sub.2 SO.sub.4 ( 2)
In this manner copper may be dissolved in aqueous medium with a yield higher than 95%.
Silver remains in the solid residue together with antimonium, arsenic and iron. That residue is highly crystaline wherefore can be easily decanted and filtered.
The copious liqueur with a residual sulphuric acidity within 15 and 30 g/l, with less than 0.3 g/l of iron and with 0.5 to 3.0 of arsenic, can be submited to a precipitation treatment of arsenic and later fitting of pH with an alkali. The resulting liquid is wholly adequated for recovering the copper either by extraction by solvents or by cementation with scrap iron, though this later technique has the advantage to supply to the solution the necessary iron so that can be recycled to the lixiviation of the concentrate.
The residue of the lixiviation is treated with a sodium-chloride solution, for giving place to a chloruret complex of silver (AgCl2 +, AgCl3 2+). The solubleness yield in this step is higher than 95%. After the copious liqueur have been removed from the lixiviation residue the cementation is initiated using zinc powder as reducing agent. The obtained product is a cement with a high silver content.
Several non limitative examples of lixiviation are afterwards given; by which will be possible to define clearly the parameters of the process in the present invention.
The equipment used in the essays are a laboratory reactor of 3.78 l, built in AISI 316L and titanium, with mechanical stirring, electrical sheet heating system, water cooling system through coil, temperature and pressure by automatic control, etc.
These essays are good to determine the influence of the iron concentration and the mass balance Fe/(As+Sb), in the results of the treatment. The values of the conditions established for the essays are the following: Pulp density: 60 Kg/m3 ; temperature: 220° C.; oxygen pressure: 600 KPAS; reaction time: 60 min.; stirring speed: 1300 rpm; concentrate composition: (in percentages) Cu 26.5; Ag 0.27; Sb 13.2; As 6.8; Fe 2.0; Zn 2.9, and S 19.4.
The results obtained are briefly shown in Table I:
______________________________________
Iron Lixiviation solub.
conc. Mass balance
yield in brine
Test no
(g/l) (Fe/As + Sb)
(Cu %) (Zn %) (Ag %)
______________________________________
1 12.8 1.05 92.7 94.2 96.2
2 18.3 1.50 95.4 95.0 95.4
3 25.6 2.10 97.3 95.6 92.3
______________________________________
As the iron concentration and consequently the mass balance Fe/(As+Sb) increases, the copper and zinc lixiviation also increases and the silver into brine solubility diminishes.
These tests are adequated to determine the influence of the pulp density in the results of the treatment.
The values of the established conditions for the experiments are the following:
Temperature: 220° C.; oxygen pressure: 600 KPAS; reaction time: 60 min.; stirring speed: 1300 rpm; iron in liquid: 12.8 g/l; concentrate composition (in percentages): Cu 26.5; Ag 0.27; Sb 13.2; As 6.8; Fe 2.0; Zn 2.9, and S 19.4.
The obtained results are shown in Table II:
______________________________________
Lixiviation Solubiliness
Pulp density solid/
yield in brine
Test no
solution Kg/m.sup.3
(Cu %) (Zn %) (Ag %)
______________________________________
1 60 92.7 94.2 96.2
2 80 91.5 94.0 97.1
3 100 89.4 94.2 98.4
______________________________________
As the pulp density increases, the copper lixiviation yield diminishes and the silver solubiliness into brine increases.
These experiments are good to determine the influence of temperature in the results of the treatment.
The values of the established conditions for the experiments are the following:
Pulp density: 100 Kg/m3 ; oxygen pressure: 600 KPAS; reaction time: 60 min.; stirring speed: 1300 rpm; iron in liquid: 21.3 g/l; concentrate composition (in percentage): Cu 26.5; Ag 0.27; Sb 13.2; As 6.8; Fe 2.0; Zn 2.9, and S 19.4.
The results obtained are shown in Table III:
______________________________________
Lixiviation Solubilyness in
Temperature yield brine
Test no
(°C.)
(Cu %) (Zn %) (Ag %)
______________________________________
1 180 76.5 90.1 90.5
2 220 92.1 93.5 95.2
______________________________________
As temperature increases, the copper and zinc lixiviation yield and the solubilyness of silver in brine also increases.
These essays are useful to determine the influence of the partial pressure of oxygen on the results of the treatment.
The values of the established conditions used in the essays are the following:
Pulp density: 60 Kg/m3 ; temperature: 220° C.; reaction time: 60 min.; stirring speed: 1300 rpm; iron in liquid: 25.6 g/l; composition of the concentrate (in percentage): Cu 26.5; Ag 0.27; Sb 13.2; As 6.8; Fe 2.0; Zn 2.9, and S 19.4.
The results obtained are briefly shown in Table IV:
______________________________________
Yield of Brine
Oxygen part. pres.
lixiviation solubleness
Test no
(KPAS) (Cu %) (Zn %) (Ag %)
______________________________________
1 300 95.8 94.7 91.0
2 600 97.3 95.6 92.3
______________________________________
When the partial pressure of oxygen increases the recoveries of copper, zinc and silver also increase.
These essays are useful to determine the influence of the stirring rate on the results of the treatment.
The values of the established conditions for the essays are the following: Pulp density: 100 Kg/m3 ; temperature: 220° C.; oxygen pressure: 600 KPAS; reaction time: 60 min.; iron in liquid: 21.3 g/l; composition of the concentrate (in percentage): Cu 26.5; Ag 0.27; Sb 13.2; As 6.8; Fe 2.0; Zn 2.9, and S 19.4.
The results obtained are shown in Table V:
______________________________________
Yield of
Stirring rate
lixiviation Brine solubleness
Test no
(rpm) (Cu %) (Zn %) (Ag %)
______________________________________
1 900 90.8 92.1 94.7
2 1300 92.1 93.5 95.2
______________________________________
When the stirring rate increases the recoveries of copper, zinc and silver rise.
These essays are useful to determine the influence of the reaction time on the results of the treatment.
The values of the established conditions used in the experiments are the following:
Pulp density: 60 Kg/m3 ; temperature 220° C.; oxygen pressure: 600 KPAS; stirring speed: 1300 rpm; iron in liquid: 12.8 g/l; composition of the concentrate (in percentages): Cu 26.5; Ag 0.27; Sb 13.2; As 6.8; Fe 2.0; Zn 2.9, and S 19.4.
The results obtained are shown in Table VI:
______________________________________
Yield of
Reaction time lixiviation Brine solubleness
Test no
(min.) (Cu %) (Zn %) (Ag %)
______________________________________
1 40 87.9 93.4 90.3
2 60 92.7 94.2 96.2
______________________________________
As can be seen when the reaction time increases the recoveries of copper, zinc and silver rise.
Claims (8)
1. A process for leaching tetrahedrite copper sulphide concentrates containing arsenic and antimony which comprises: slurrying the tetrahedrite copper concentrate in a ferrous sulphate aqueous solution to obtain a solid-liquid ratio higher than 40 Kg of solids per cubic meter of solution; subjecting said slurry to an oxidation leach in a stirred pressure reactor at an oxygen partial pressure higher than 3 Kg/cm2 and a temperature in the range of from 140° C. to 250° C. for complete oxidation of metal sulphides to sulphates and precipitation of iron as ferric arseniate and ferric antimoniate; separating the reaction mixture into a solid residue containing the ferric arseniate and ferric antimoniate and insoluble non-ferrous metal sulphates, and a leach liquor containing sulphuric acid, and copper sulphate; and recovering the metal from the leach liquor and from the solid residue.
2. A process according to claim 1 wherein the iron concentration in the ferrous sulphate leaching solution is in the range of from 1 to 50 grams per liter, and the mass ratio of iron to arsenic plus antimony is above 0.5.
3. A process according to claim 1 wherein the solid-liquid ratio of the leaching slurry is from 60 to 100 Kg of tetrahedrite copper concentrate per cubic meter of ferrous sulphate leaching solution.
4. A process according to claim 1 wherein the oxidation leach reaction of the tetrahedrite copper concentrate slurry in ferrous sulphate solution is carried out at a temperature of from 210° C. to 230° C.
5. A process according to claim 1 wherein the oxidation leach reaction of the tetrahedrite copper concentrate slurry in ferrous sulphate solution is carried out at constant pressure with an oxygen partial pressure of from about 5 to about 7 Kg/cm2.
6. A process according to claim 1 wherein the oxidation leach reaction of the tetrahedrite concentrate slurry in ferrous sulphate solution is carried out with stirring to produce a dispersion of the oxygen in the reacting slurry.
7. A process according to claim 1 wherein the conditions of oxidation leach reaction of the tetrahedrite concentrate slurry in ferrous sulphate solution are constant not only until all the metal sulphides are oxidized to sulphates but also until all the iron is precipitated as ferric arseniate, ferric antimoniate, and ferric oxide, which is achieved in a residence time equivalent to a reaction time in the range of from about 30 to 60 minutes.
8. A process according to claim 1 wherein the step of recovering said metals comprises introducing scrap iron into said resultant leach liquor containing sulphuric acid and copper sulphate to produce cementation of said copper and to yield an aqueous solution comprising ferrous sulphate, and recycling said ferrous sulphate solution for use in said step of slurrying tetrahedrite copper.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ES526235A ES8504266A1 (en) | 1983-10-04 | 1983-10-04 | Process for leaching sulphide concentrates of the tetrahedrite type containing high concentrations of arsenic and antimony |
| ES526.235 | 1983-10-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4610723A true US4610723A (en) | 1986-09-09 |
Family
ID=8486291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/656,740 Expired - Fee Related US4610723A (en) | 1983-10-04 | 1984-10-01 | Process for leaching sulphide concentrates of the tetrahedrite type containing high concentrations of arsenic and antimony |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US4610723A (en) |
| ES (1) | ES8504266A1 (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5137640A (en) * | 1991-05-06 | 1992-08-11 | Allied-Signal Inc. | Process for the separation of arsenic acid from a sulfuric acid-containing solution |
| WO1994009165A1 (en) * | 1992-10-16 | 1994-04-28 | Sunshine Mining Company | Antimony separation process |
| US5415847A (en) * | 1993-06-22 | 1995-05-16 | Gem, Inc. | Treatment of pit waste containing chromated copper arsenate |
| WO2007045034A1 (en) * | 2005-10-19 | 2007-04-26 | Dundee Precious Metals Inc | Process for recovery of metal values from materials containing arsenic and/or antimony |
| US9885095B2 (en) | 2014-01-31 | 2018-02-06 | Goldcorp Inc. | Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate |
| US10544482B2 (en) | 2015-07-06 | 2020-01-28 | Sherritt International Corporation | Recovery of copper from arsenic-containing process feed |
| US11118244B2 (en) | 2017-04-14 | 2021-09-14 | Sherritt International Corporation | Low acidity, low solids pressure oxidative leaching of sulphidic feeds |
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|---|---|---|---|---|
| US2686114A (en) * | 1951-01-19 | 1954-08-10 | Chemical Construction Corp | Elimination of arsenic from metallic arsenide-sulfide concentrates |
| US3218161A (en) * | 1961-02-27 | 1965-11-16 | Sherritt Gordon Mines Ltd | Process for the precipitation of metal values from solutions |
| US3709680A (en) * | 1971-07-09 | 1973-01-09 | Sunshine Mining Co | Process for removal of arsenic from sulfo-ore |
| US3891522A (en) * | 1972-02-28 | 1975-06-24 | Cominco Ltd | Hydrometallurgical process for treating copper-iron sulphides |
| US3911078A (en) * | 1972-09-20 | 1975-10-07 | Little Inc A | Method for removing arsenic and antimony from copper ore concentrates |
| US3957602A (en) * | 1974-07-24 | 1976-05-18 | Cyprus Metallurgical Processes Corporation | Recovery of copper from chalcopyrite utilizing copper sulfate leach |
| US3964901A (en) * | 1973-10-19 | 1976-06-22 | Sherritt Gordon Mines Limited | Production of copper and sulfur from copper-iron sulfides |
| US3969202A (en) * | 1975-06-02 | 1976-07-13 | Asarco Incorporated | Process for the recovery of antimony values from ores containing sulfo-antimony compounds of copper, and arsenic |
| US4220627A (en) * | 1977-11-28 | 1980-09-02 | Outokumpu Oy | Process for the treatment of raw materials containing arsenic and metal |
| US4438079A (en) * | 1981-03-30 | 1984-03-20 | Sumitomo Metal Mining Company Limited | Method for manufacture of arsenious anhydride |
-
1983
- 1983-10-04 ES ES526235A patent/ES8504266A1/en not_active Expired
-
1984
- 1984-10-01 US US06/656,740 patent/US4610723A/en not_active Expired - Fee Related
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2686114A (en) * | 1951-01-19 | 1954-08-10 | Chemical Construction Corp | Elimination of arsenic from metallic arsenide-sulfide concentrates |
| US3218161A (en) * | 1961-02-27 | 1965-11-16 | Sherritt Gordon Mines Ltd | Process for the precipitation of metal values from solutions |
| US3709680A (en) * | 1971-07-09 | 1973-01-09 | Sunshine Mining Co | Process for removal of arsenic from sulfo-ore |
| US3891522A (en) * | 1972-02-28 | 1975-06-24 | Cominco Ltd | Hydrometallurgical process for treating copper-iron sulphides |
| US3911078A (en) * | 1972-09-20 | 1975-10-07 | Little Inc A | Method for removing arsenic and antimony from copper ore concentrates |
| US3964901A (en) * | 1973-10-19 | 1976-06-22 | Sherritt Gordon Mines Limited | Production of copper and sulfur from copper-iron sulfides |
| US3957602A (en) * | 1974-07-24 | 1976-05-18 | Cyprus Metallurgical Processes Corporation | Recovery of copper from chalcopyrite utilizing copper sulfate leach |
| US3969202A (en) * | 1975-06-02 | 1976-07-13 | Asarco Incorporated | Process for the recovery of antimony values from ores containing sulfo-antimony compounds of copper, and arsenic |
| US4220627A (en) * | 1977-11-28 | 1980-09-02 | Outokumpu Oy | Process for the treatment of raw materials containing arsenic and metal |
| US4438079A (en) * | 1981-03-30 | 1984-03-20 | Sumitomo Metal Mining Company Limited | Method for manufacture of arsenious anhydride |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5137640A (en) * | 1991-05-06 | 1992-08-11 | Allied-Signal Inc. | Process for the separation of arsenic acid from a sulfuric acid-containing solution |
| WO1994009165A1 (en) * | 1992-10-16 | 1994-04-28 | Sunshine Mining Company | Antimony separation process |
| US5415847A (en) * | 1993-06-22 | 1995-05-16 | Gem, Inc. | Treatment of pit waste containing chromated copper arsenate |
| WO2007045034A1 (en) * | 2005-10-19 | 2007-04-26 | Dundee Precious Metals Inc | Process for recovery of metal values from materials containing arsenic and/or antimony |
| US20090019970A1 (en) * | 2005-10-19 | 2009-01-22 | Dundee Precious Metals Inc. | Process for recovery of metal values from materials containing arsenic and/or antimony |
| US9885095B2 (en) | 2014-01-31 | 2018-02-06 | Goldcorp Inc. | Process for separation of at least one metal sulfide from a mixed sulfide ore or concentrate |
| US10370739B2 (en) | 2014-01-31 | 2019-08-06 | Goldcorp, Inc. | Stabilization process for an arsenic solution |
| US11124857B2 (en) | 2014-01-31 | 2021-09-21 | Goldcorp Inc. | Process for separation of antimony and arsenic from a leach solution |
| US10544482B2 (en) | 2015-07-06 | 2020-01-28 | Sherritt International Corporation | Recovery of copper from arsenic-containing process feed |
| US11118244B2 (en) | 2017-04-14 | 2021-09-14 | Sherritt International Corporation | Low acidity, low solids pressure oxidative leaching of sulphidic feeds |
Also Published As
| Publication number | Publication date |
|---|---|
| ES526235A0 (en) | 1985-04-01 |
| ES8504266A1 (en) | 1985-04-01 |
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